DE3319099A1 - ALUMINUM CATALYST AND METHOD FOR THE PRODUCTION AND APPLICATION THEREOF - Google Patents

Description

Description

Alumina catalyst and process for its manufacture

and application

Catalysts based on γ-alumina are known; is also known to be responsible for certain reactions, have too high an acidity, especially for the bond isomerization reactions. In addition, increases the acidity of γ-alumina continues when this increases the thermal stability has been treated with silica (US-PS 40 13 590 and 40 13 589 as well US Re 30668). On the other hand, stabilization with silica is necessary in order to regenerate alumina 0 accessible at high temperature without loss of their activity.

Surprisingly, it was found that, on the one hand, the acidity of catalysts based on γ-aluminum oxide can be reduced so far that it is suitable for isomerization reactions and on the other hand is not reduced to such an extent that the thermal stability would be called into question. This is achieved according to the invention by adding one or more oxide (s)

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from metals of group II A and / or VIII and / or III B and / or the lanthanides to stabilized with silica γ-alumina.

The catalyst according to the invention can be the general formula

a Al ₃ O ₃ . b SiO ₂ - c Me 0

ascribing, in which Me 0 is one or more oxide (s) of

χ y

Metals of groups II A, III B, VIII and / or the lanthanides and a, b and c denote the Specify the number of moles of oxidic components, with the relation

>
c = mb + B

must be fulfilled;

B = 0.01,

b = 0.02 to 0.25, "

(b + c) / a = 0.01 to 9, *

m = 0.7 to 0.1.

In the case of a calcium-containing catalyst, the molar ratio should be satisfy the following relationship:

Moles CaO = 0.500 - moles SiO ₂ + 0.03 0.

In the case of a barium-containing catalyst, the molar ratio should satisfy the following relationship;

Moles of BaO = 0.500. Moles SiO ₂ + 0.020 «

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In the case of catalysts containing lanthanum, the molar ratio should be satisfy the following relationship:

Moles of La ₂ O ₃ = 0.257. Moles of SiO ₂ + 0.014.5

In the case of iron-containing catalysts, the molar ratio should satisfy the following relationship;

Moles of Fe ₂ O ₃ = 0.290. Moles of SiO ₂ + 0.018. 10

In the above four special cases, the number of moles SiO ^ and the ratio {b + c) / a are as given above Values.

The catalyst according to the invention is particularly suitable for the isomerization of olefinic double bonds, in particular for the isomerization of 2-butene to! -butene.

The stabilized γ-alumina catalyst according to the invention is prepared in the sense of the above American patents by impregnating the alumina with an aqueous solution of salts of the metals of groups II A, III B, VIII and / or the lanthanides, preferably nitrates or acetates.
25th

The invention is further illustrated by the following examples.

Example Ί

20 g of γ-clay (specific surface 200 m ² / g) were ^{treated with 15 cm 3 of} an alcoholic solution containing 0.75 g of "Dynasil A 40", that is a 40% solution of ethylene orthosilicate.

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The mixture was allowed to ^{react at 50 °} C. for 2 h, then / decanted and treated with steam to hydrolyze the silanol groups. This was followed by drying and firing at 500 ° C. for 4 hours.

A material containing 1.5% SiO ₂ r was obtained which was ^{impregnated with 15 cm 3 of} an aqueous solution of 5.9 g of lanthanum nitrate, the impregnated material was dried and ^{fired at 500 °} C. for 4 h.

The catalyst obtained in this way was one with 1.5% SiO ~ stabilized γ-clay containing 10%

It was introduced into a reactor and isomerized in this trans-2-butene at 47 0 ⁰ C under atmospheric pressure at a throughput rate of 6 m ³ / m ³ .h. In this way, 1-butene was obtained with only 140 ppm of isobutene.

After 24 h at 1,000 ^° C., the catalyst had a specific surface area of 113 m ⁷ / g and after 40 cycles of operating time - a total of 332 h - and regeneration

all in all, ....

time - / T52 h - no loss of activity. The regeneration took place at a temperature of 540 ^° C.

Example 2

According to Example 1, a catalyst was prepared which _{contained 1.5% SiO 2} and 2.5% CaO in γ-alumina. The calcium content was introduced by soaking with 15 cm ^{3 of} an aqueous solution of 2.4 g of calcium nitrate, drying and firing at 500 ^° C. for 4 h.

This catalyst was used, as above, for the isomerization of 2-butene at 450 ⁰ C under atmospheric pressure at a flow rate of 6 m ³ / m ³ .h, yielding! Butene received ppm with an isobutene content of only 150th

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After a heat treatment of 24 h bei.l 000 ⁰ C, the catalyst had a specific surface area of 183 in ² / g and 'showed after 40 cycles of operation time - a total of 332 h and regeneration time - a total of 152 h - no loss of activity. The regeneration took place at 540 ^° C.

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Claims (7)

• · * ft • · PATENT LAWYERS ·· '''·· WUESTHOFF- ν. PECHMANN -BEHRENS- EUROPEAN PATENT ATTORNEYS DR.-ING. FRANZ TUESTHOFF DR. PHIL. FREDA TUESTHOFF (1927-1956) DIPU-INC. GEKHAKD PULSE (lJJI-IJ / l) DIPL.-CHEM. DR. £. PREIH ERR FROM PECHM DR.-ING. DIETER BEHRENS DIPL.-ING .; D1PL - V1RTSCH.-1NG. RUPERT < lA-57 248 Note: SNAMPROGETTI S.p.A. D-8000 MUNICH SCHWEIGERSTRASSE phone: (0S9) 66 20 ji TELEGRAM: PROTECT PATENT telex: j 24070 Patent claims Ύ-alumina catalyst of the general formula a Al ₂ O ₃ . b SiO ₂ - c Me 0 _t 5 wherein Me 0 is one or more oxide (s) of metals Group II A, III B VIII and / or of the lanthanides means, a, b and c the number of moles of the oxide components indicates and the relationship c = m.b + B holds where B = 0.01, b 0.020 to 0.25, (b + c) / a 0.01 to 9 and m are 0.7 to 0.1. 2. Catalyst according to claim 1, characterized in that Me O La ₉ O ^. is and the relation Mole La ₃ O ₃ = 0.257. Moles of SiO ₂ + 0.014 is applicable. 3. Catalyst according to Claim 1, characterized in that Μβ _χ 0 F ^e 2 ° 3 ^{and the} ratio of moles Fe ₂ O ₃ = 0.290. Moles of SiO ₃ + 0.018 is applicable. / 2 LA-57 248 - '2 - 4. Catalyst according to claim l, characterized in that Me 0 is CaO and the relation Moles of CaO = 0.500. Moles of SiO ₂ + 0.030 is applicable. 5. Catalyst according to claim 1, characterized in that Me 0 is BaO and the relation 10 Moles of BaO = 0.50.0. Moles of SiO ₂ + 0.020 is applicable. 6. A process for the preparation of the catalysts according to claim 1 to 5, stabilized with silica, thereby characterized in that the γ-alumina stabilized with silica is mixed with an aqueous solution impregnated with salts of metals of groups II A, III B, VIII and / or lanthanides. 7. Use of the catalysts according to Claims 1 to 5 for the isomerization of olefinically unsaturated compounds. 8149